CN112810271A - Resin film, laminated film, optical member, display member, front panel, and method for producing laminated film - Google Patents
Resin film, laminated film, optical member, display member, front panel, and method for producing laminated film Download PDFInfo
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- CN112810271A CN112810271A CN202110045625.XA CN202110045625A CN112810271A CN 112810271 A CN112810271 A CN 112810271A CN 202110045625 A CN202110045625 A CN 202110045625A CN 112810271 A CN112810271 A CN 112810271A
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- laminated film
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- 230000037303 wrinkles Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Images
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
- H10K77/10—Substrates, e.g. flexible substrates
- H10K77/111—Flexible substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
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- H10K50/844—Encapsulations
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/87—Passivation; Containers; Encapsulations
- H10K59/873—Encapsulations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/102—Oxide or hydroxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/04—Treatment by energy or chemical effects using liquids, gas or steam
- B32B2310/0445—Treatment by energy or chemical effects using liquids, gas or steam using gas or flames
- B32B2310/0463—Treatment by energy or chemical effects using liquids, gas or steam using gas or flames other than air
- B32B2310/0481—Ozone
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2310/00—Treatment by energy or chemical effects
- B32B2310/08—Treatment by energy or chemical effects by wave energy or particle radiation
- B32B2310/0806—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation
- B32B2310/0831—Treatment by energy or chemical effects by wave energy or particle radiation using electromagnetic radiation using UV radiation
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K2102/00—Constructional details relating to the organic devices covered by this subclass
- H10K2102/301—Details of OLEDs
- H10K2102/311—Flexible OLED
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- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/841—Self-supporting sealing arrangements
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/85—Arrangements for extracting light from the devices
- H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
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- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/40—OLEDs integrated with touch screens
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- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/80—Constructional details
- H10K59/875—Arrangements for extracting light from the devices
- H10K59/879—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
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- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
Disclosed is a laminated film comprising a resin film containing a polyimide-based polymer, and a functional layer provided on at least one main surface side of the resin film. Also disclosed is a resin film containing a polyimide-based polymer and a silicon material containing silicon atoms, wherein the atomic ratio of silicon atoms to nitrogen atoms, i.e., Si/N, on at least one main surface is 8 or more.
Description
The present application is a divisional application of an application having an application number of 201580060423.5 filed by the applicant under the name of "resin film, laminated film, optical member, display member, front panel, and method for manufacturing laminated film". The parent application date was 2015, 11, month 06, and the earliest priority date was 2014, 11, month 10.
Technical Field
The invention relates to a resin film, a laminated film, an optical member, a display member, a front panel, and a method for manufacturing the laminated film.
Background
Glass has been conventionally used as a base material for various display members such as solar cells and displays. However, glass has a disadvantage of being easily broken and heavy, and does not necessarily have sufficient material properties for the recent thinning, weight reduction, and flexibility of displays. Therefore, as a material to replace glass, acrylic resins and laminated films in which scratch resistance is imparted to the resins have been studied. Further, composite materials of an organic material and an inorganic material, such as a composite film containing polyimide and silica, have been studied (see, for example, patent documents 1 and 2).
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2008-163309
Patent document 2: specification of U.S. Pat. No. 8207256
Disclosure of Invention
Problems to be solved by the invention
A laminated film having a known acrylic resin as a base material and a functional layer provided on the base material is not necessarily sufficient in terms of flexibility in order to be used as a display member or a front panel of a flexible device.
Accordingly, an object of one aspect of the present invention is to provide a laminated film having excellent bendability.
In addition, in order to use the laminated film as a display member or a front panel of a flexible device, it is also required to have good visibility when bent. However, even a laminated film having excellent flexibility causes changes in contrast and color tone when bent.
Accordingly, another aspect of the present invention is directed to improve the visibility at the time of bending of a laminated film having a functional layer.
In order to use a composite film containing a polyimide-based polymer and silica as a flexible member, it is generally necessary to form functional layers having various functions such as an optical adjustment function and an adhesion function on the composite film. However, when a functional layer is formed on a composite film, the adhesion between the functional layer and the composite film may not be sufficient.
Therefore, another object of the present invention is to provide a resin film having excellent adhesion to various functional layers, and a laminated film using the same.
According to the present invention, there are also provided an optical member, a display member, and a front panel for a flexible device, each using the laminated film.
Means for solving the problems
A multilayer film according to one embodiment of the present invention includes a resin film (resin substrate) containing a polyimide-based polymer, and a functional layer provided on at least one main surface side of the resin film.
In the laminated film according to one embodiment of the present invention, the silicon material may be silicon dioxide particles.
When a light irradiation test in which 313nm light is irradiated to a laminated film for 24 hours from the functional layer side is performed by a light source having an output of 40W provided at a distance of 5cm from the laminated film of one embodiment, the laminated film may satisfy the following conditions:
(i) the laminated film after the light irradiation test has a transmittance of 85% or more for light of 550 nm; and
(ii) the laminated film before the light irradiation test has a yellowness index of 5 or less, and the difference in yellowness index before and after the light irradiation test of the laminated film is less than 2.5.
The resin film after the light irradiation test may have a haze of 1.0% or less.
In the laminated film napkin according to one embodiment of the present invention, the functional layer may be a layer having at least 1 function selected from the group consisting of ultraviolet absorption, surface hardness, adhesiveness, color tone adjustment, and refractive index adjustment.
In the multilayer film according to one embodiment of the present invention, the functional layer may be a layer having at least one of ultraviolet absorption and surface hardness.
The resin film according to one embodiment of the present invention contains a polyimide polymer and a silicon material containing silicon atoms. The atomic ratio of silicon atoms to nitrogen atoms, i.e., Si/N, in at least one main surface of the resin film may be 8 or more. The silicon material may be silicon dioxide particles.
A laminated film according to an embodiment of the present invention includes a resin film according to an embodiment of the present invention, and a functional layer provided on a main surface side of the resin film, the main surface side having an Si/N ratio of 8 or more.
In the laminated film according to one embodiment of the present invention, a primer layer may be provided between the resin film and the functional layer. The primer layer may contain a silane coupling agent. The silane coupling agent may have at least 1 substituent selected from a methacryloyl group, an acryloyl group, and an amino group.
An optical member according to one embodiment of the present invention includes the laminated film of the present invention. A display member according to one embodiment of the present invention includes the laminated film of the present invention. A front panel according to one embodiment of the present invention includes the laminate film of the present invention.
Effects of the invention
According to the present invention, a laminated film having excellent bendability can be provided. The laminated film of the present invention can have functions such as transparency, ultraviolet ray resistance, and surface hardness required when applied to an optical member, a display member, or a front panel of a flexible device. According to the present invention, a laminated film excellent in visibility when bent can be provided.
According to the present invention, a resin film having excellent adhesion to various functional layers, a laminated film using the resin film, and a method for producing the laminated film can be provided. The present invention can also provide an optical member, a display member, and a front panel using the laminated film. The resin film obtained in the present invention can have excellent transparency and bendability.
Drawings
Fig. 1 is a schematic sectional view showing a resin film according to a first embodiment.
Fig. 2 is a schematic sectional view showing a laminated film according to a second embodiment.
Fig. 3 is a schematic cross-sectional view showing a laminated film of a third embodiment.
Fig. 4 is a schematic cross-sectional view showing an example of a display device.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.
[ first embodiment ]
Fig. 1 is a schematic sectional view showing a resin film of the present embodiment. The resin film 10 of the present embodiment contains a polyimide-based polymer and has a pair of main surfaces 10a and 10b facing each other.
The polyimide-based polymer contained in the resin film 10 may be polyimide. The polyimide is, for example, a condensation type polyimide obtained by polycondensation using diamines and tetracarboxylic dianhydrides as starting materials. As the polyimide-based polymer, a polyimide-based polymer that is soluble in a solvent used for forming a resin film can be selected.
The diamine is not particularly limited, and aromatic diamines, alicyclic diamines, aliphatic diamines, and the like, which are generally used in the synthesis of polyimide, can be used. The diamines may be used alone or in combination of 2 or more.
As the tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, acyclic aliphatic tetracarboxylic dianhydride, and the like can be used, and there is no particular limitation. The tetracarboxylic dianhydrides may be used alone or in combination of 2 or more. Instead of the tetracarboxylic dianhydride, a tetracarboxylic acid compound selected from tetracarboxylic acid compound analogs such as an acid chloride compound may be used as a starting material.
At least one of the diamines and the tetracarboxylic acid compounds (tetracarboxylic acid dianhydrides) may have 1 or more functional groups selected from at least 1 kind of functional groups selected from fluorine-based substituents, hydroxyl groups, sulfone groups, carbonyl groups, heterocycles, and long-chain alkyl groups having 1 to 10 carbon atoms. Among them, diamines and tetracarboxylic acid compounds (tetracarboxylic dianhydrides) may have a fluorine-based substituent introduced as a functional group from the viewpoint of transparency. The fluorine-based substituent may be any group containing a fluorine atom, and specific examples thereof include a fluorine group (fluorine atom, -F) and a trifluoromethyl group.
From the viewpoint of solubility in a solvent, transparency when forming the resin film 10, and bendability, an alicyclic tetracarboxylic acid compound (alicyclic tetracarboxylic dianhydride or the like) or an aromatic tetracarboxylic acid compound (aromatic tetracarboxylic dianhydride or the like) may be used as the tetracarboxylic acid compound. From the viewpoint of transparency and suppression of coloring of the resin film, an alicyclic tetracarboxylic acid compound or an aromatic tetracarboxylic acid compound having a fluorine-based substituent may be used as the tetracarboxylic dianhydride.
As the diamine, an aromatic diamine, an alicyclic diamine, or an aliphatic diamine may be used alone, or 2 or more kinds thereof may be used in combination. From the viewpoints of solubility in a solvent, transparency when forming the resin film 10, and flexibility, an alicyclic diamine or an aromatic diamine may be used as the diamine. From the viewpoint of transparency and suppression of coloring of the resin film, as the diamine, an alicyclic diamine or an aromatic diamine having a fluorine-based substituent may be used.
When a polyimide-based polymer is used, a resin film having particularly excellent flexibility, high light transmittance (for example, 85% or more or 88% or more with respect to light of 550 nm), low yellowness (YI value, for example, 5% or less or 3% or less), and low haze (for example, 1.5% or less or 1.0% or less) can be easily obtained.
The polyimide may have a repeating structural unit represented by the following formula (PI). Here, G is a 4-valent organic group, and a is a 2-valent organic group.
Chemical formula 1
Examples of G include a 4-valent organic group selected from a non-cyclic aliphatic group, a cyclic aliphatic group, and an aromatic group. G may be a cyclic aliphatic group or an aromatic group. Examples of the aromatic group include a monocyclic aromatic group, a condensed polycyclic aromatic group, and a non-condensed polycyclic aromatic group having 2 or more aromatic rings and connecting these groups to each other directly or via a linking group. From the viewpoint of transparency and suppression of coloring of the resin film, G may be a cyclic aliphatic group, or a cyclic aliphatic group, a monocyclic aromatic group, a condensed polycyclic aromatic group or a non-condensed polycyclic aromatic group having a fluorine-based substituent. More specifically, there may be mentioned saturated or unsaturated cycloalkyl groups, saturated or unsaturated heterocycloalkyl groups, aryl groups, heteroaryl groups, arylalkyl groups, alkylaryl groups, heteroarylalkyl groups, and groups having any 2 groups (which may be the same) among them and connecting them to each other directly or via a linking group. Examples of the linking group include-O-, an alkylene group having 1 to 10 carbon atoms, and-SO2-, -CO-or-CO-NR- (R represents an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, or a hydrogen atom). The number of carbon atoms of G is usually 2 to 32, and may be 2 to 27, 5 to 10, 6 to 8, or 3 to 8. When G is a cyclic aliphatic group or an aromatic group, a part of carbon atoms may be substituted with a hetero atom. Examples of G are saturated or unsaturated cycloalkyl, saturated or unsaturated heterocycloalkyl, which may have 3 to 8 carbon atoms.Examples of heteroatoms include O, N and S.
Specifically, G may be a group represented by the following formula (20), formula (21), formula (22), formula (23), formula (24), formula (25) or formula (26). Wherein represents a bonding terminal. Z represents a single bond, -O-, -CH2-、-C(CH3)2-、-Ar-O-Ar-、-Ar-CH2-Ar-、-Ar-C(CH3)2-Ar-or-Ar-SO2-Ar-. Ar represents an aryl group having 6 to 20 carbon atoms, and an example thereof is a phenylene group (benzene ring). At least 1 of the hydrogen atoms of these groups may be substituted with a fluorine-based substituent.
Chemistry 2
Examples of A include organic groups having a valence of 2 selected from acyclic aliphatic groups, cyclic aliphatic groups, and aromatic groups. The 2-valent organic group represented by a may be a cyclic aliphatic group or an aromatic group. Examples of the aromatic group include monocyclic aromatic groups, condensed polycyclic aromatic groups, and non-condensed polycyclic aromatic groups having 2 or more aromatic rings and connected to each other directly or via a linking group. From the viewpoint of transparency and suppression of coloring of the resin film, a fluorine-based substituent may be introduced into at least a part of a.
More specifically, a includes a saturated or unsaturated cycloalkyl group, a saturated or unsaturated heterocycloalkyl group, an aryl group, a heteroaryl group, an arylalkyl group, an alkylaryl group, a heteroarylalkyl group, and a group having any 2 groups (which may be the same) of them and connecting them to each other directly or via a linking group. Examples of the hetero atom include O, N and S. Examples of the linking group include-O-, an alkylene group having 1 to 10 carbon atoms, and-SO2-, -CO-, and-CO-NR- (R represents an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, and a propyl group, or a hydrogen atom).
The number of carbon atoms of the 2-valent organic group represented by A is usually 2 to 40, and may be 5 to 32, 12 to 28, or 24 to 27.
Specifically, a may be a group represented by the following formula (30), formula (31), formula (32), formula (33), or formula (34). Wherein represents a bonding terminal. Z1、Z2And Z3May each independently be a single bond, -O-, -CH2-、-C(CH3)2-、-SO2-, -CO-or-CO-NR- (R represents an alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group or a propyl group, or a hydrogen atom). In the following groups, Z1And Z2And Z2And Z3Preferably in the meta or para position, respectively, with respect to the rings. In addition, Z1Single bond to terminal, Z2A single bond to the terminal, and Z3The single bond to the terminal is preferably in the meta or para position. 1 example is Z1And Z3is-O-and Z2is-CH2-、-C(CH3)2-or-SO2-. At least 1 of the hydrogen atoms of these groups may be substituted with a fluorine-based substituent.
Chemistry 3
At least one of A and G may have at least 1 hydrogen atom substituted with at least 1 functional group selected from a fluorine-containing substituent such as a fluorine group and a trifluoromethyl group, a hydroxyl group, a sulfone group, an alkyl group having 1 to 10 carbon atoms, and the like. When a and G are each a cyclic aliphatic group or an aromatic group, at least one of a and G may have a fluorine-based substituent, or both a and G may have a fluorine-based substituent.
The polyimide-based polymer may be a polymer containing at least 1 repeating structural unit represented by formula (PI), formula (a') or formula (b). G in the formula (a)2Represents an organic group having a valence of 3, A2Represents an organic group having a valence of 2. G in the formula (a')3Represents a 4-valent organic group, A3Represents an organic group having a valence of 2. G in the formula (b)4And A4Each represents a 2-valent organic group.
Chemistry 4
In addition to being a 3-valent group, G in formula (a)2May be selected from the same groups as G in formula (PI). For example, G2Specific examples of G include those in which 1 of 4 bonding terminals in the group represented by the formulae (20) to (26) is substituted with a hydrogen atom. A in the formula (a)2May be selected from the same groups as A in the formula (PI).
G in the formula (a')3May be selected from the same groups as G in formula (PI). A in the formula (a')3May be selected from the same groups as A in the formula (PI).
G in the formula (b) is not limited to a 2-valent group4May be selected from the same groups as G in formula (PI). For example, G4Specific examples of G include those in which 2 of 4 bonding terminals in the group represented by the formulae (20) to (26) are substituted with a hydrogen atom. A in the formula (b)4May be selected from the same groups as A in the formula (PI).
The polyimide-based polymer containing at least 1 type of polymer of the repeating structural unit represented by the formula (PI), the formula (a') or the formula (b) may be a condensation-type polymer obtained by condensation-polymerizing at least 1 type of diamine with a tetracarboxylic acid compound or a tricarboxylic acid compound (including tricarboxylic acid compound analogs such as an acid chloride compound and a tricarboxylic acid anhydride). As the starting material, in addition to these, a dicarboxylic acid compound (including an acid chloride compound and the like) may be used in some cases. The repeating structural unit represented by the formula (a') is generally derived from diamines and tetracarboxylic acid compounds. The repeating structural unit represented by the formula (a) is generally derived from diamine and tricarboxylic acid compounds. The repeating structural unit represented by the formula (b) is usually derived from diamines and dicarboxylic acid compounds. Specific examples of the diamines and tetracarboxylic acid compounds are as described above.
Examples of the tricarboxylic acid compound include an aromatic tricarboxylic acid, an alicyclic tricarboxylic acid, an acyclic aliphatic tricarboxylic acid, and a chloride compound or an acid anhydride similar thereto. The tricarboxylic acid compound may also be an acid chloride compound of an aromatic tricarboxylic acid, an alicyclic tricarboxylic acid, a non-cyclic aliphatic tricarboxylic acid, or a similar compound thereof. The tricarboxylic acid compound may be used in combination of 2 or more.
The tricarboxylic acid compound may be selected from alicyclic tricarboxylic acid compounds and aromatic tricarboxylic acid compounds from the viewpoint of solubility in a solvent, transparency when forming the resin film 10, and bendability. From the viewpoint of transparency and suppression of coloring of the resin film, the tricarboxylic acid compound may include an alicyclic tricarboxylic acid compound having a fluorine-based substituent and an aromatic tricarboxylic acid compound having a fluorine-based substituent.
Examples of the dicarboxylic acid compound include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, acyclic aliphatic dicarboxylic acids, and their analogous acid chloride compounds and acid anhydrides. The dicarboxylic acid compound may be an acid chloride compound of an aromatic dicarboxylic acid, an alicyclic dicarboxylic acid, a non-cyclic aliphatic dicarboxylic acid, or the like. The dicarboxylic acid compound may be used in combination of 2 or more.
The dicarboxylic acid compound may be selected from alicyclic dicarboxylic acid compounds and aromatic dicarboxylic acid compounds from the viewpoint of solubility in a solvent, transparency when forming the resin film 10, and bendability. The dicarboxylic acid compound may be selected from alicyclic dicarboxylic acid compounds having a fluorine-based substituent and aromatic dicarboxylic acid compounds having a fluorine-based substituent, from the viewpoint of transparency of the resin film and suppression of coloration.
The polyimide-based polymer may be a copolymer containing a plurality of different types of the above-mentioned repeating units. The polyimide polymer has a weight average molecular weight of 10000 to 500000. The polyimide polymer may have a weight average molecular weight of 50000 to 500000, 100000 to 500000 or 70000 to 400000. The weight average molecular weight is a molecular weight in terms of standard polystyrene measured by GPC. If the weight average molecular weight of the polyimide polymer is large, high bendability tends to be easily obtained, and if the weight average molecular weight of the polyimide polymer is too large, viscosity of the varnish tends to be high, and processability tends to be low.
The polyimide-based polymer may contain a halogen atom such as a fluorine atom which may be introduced with the above-mentioned fluorine-based substituent or the like. When the polyimide-based polymer contains a halogen atom, the elastic modulus of the resin film can be increased, and the yellowness can be reduced. This can suppress the occurrence of scratches, wrinkles, and the like in the resin film, and can improve the transparency of the resin film. For example, the fluorine atom can be introduced into the molecule of the polyimide (polyimide-based polymer) by using a compound having a fluorine-based substituent such as a fluorine group or a trifluoromethyl group as at least one of the diamine group and the tetracarboxylic dianhydride. The content of the halogen atom (or fluorine atom) in the polyimide may be 1 to 40% by mass, or 1 to 30% by mass, based on the mass of the polyimide-based polymer.
The resin film 10 may further contain an inorganic material such as inorganic particles. The inorganic material may be a silicon material containing silicon atoms. By containing an inorganic material such as a silicon material in the resin film 10, a particularly excellent effect can be obtained in terms of bendability.
Examples of the silicon material containing a silicon atom include silicon dioxide particles, and silicon compounds such as quaternary alkoxysilane such as Tetraethylorthosilicate (TEOS). The silicon material may be silica particles from the viewpoint of transparency and flexibility of the resin film 10.
The average primary particle diameter of the silica particles may be 10nm to 100nm, or 20nm to 80 nm. When the average primary particle diameter of the silica particles is 100nm or less, the transparency tends to be improved. When the average primary particle diameter of the silica particles is 10nm or more, the strength of the resin film tends to be improved, and the cohesive force of the silica particles tends to be weakened, whereby handling tends to be easy.
The (average) primary particle diameter of the silica particles in the resin film can be determined by observation with a Transmission Electron Microscope (TEM). The particle distribution of the silica particles before forming the resin film can be determined by a commercially available laser diffraction particle size distribution meter.
In the resin film 10, the mixing ratio of the polyimide and the inorganic material (silicon material) may be 1: 9 to 10: 0 or 1: 9 to 9: 1, or 3: 7 to 10: 0 or 3: 7 to 8: 2 in terms of mass ratio. The mixing ratio can also be 3: 7-8: 2, or 3: 7-7: 3. The proportion of the inorganic material with respect to the total mass of the polyimide and the inorganic material is usually 20 mass% or more, and may be 30 mass% or more. The proportion is usually 90 mass% or less, and may be 70 mass% or less. When the mixing ratio of the polyimide and the inorganic material (silicon material) is within the above range, the transparency and mechanical strength of the resin film tend to be improved.
The resin film 10 may further contain components other than polyimide and an inorganic material (silicon material) within a range where transparency and bendability are not significantly impaired. Examples of the components other than the polyimide and the inorganic material (silicon material) include an antioxidant, a release agent, a stabilizer, a bluing agent, a flame retardant, a lubricant, and a leveling agent. The total ratio of the polyimide and the inorganic material may be more than 0% and 20% by mass or less, or more than 0% and 10% by mass or less, based on the mass of the resin film 10.
When the resin film 10 contains a polyimide and a silicon material, the atomic ratio of silicon atoms to nitrogen atoms, i.e., Si/N, in at least one main surface 10a may be 8 or more. The atomic ratio Si/N is a value calculated from the amount of silicon atoms and the amount of nitrogen atoms present, which are obtained by evaluating the composition of the main surface 10a by X-ray Photoelectron Spectroscopy (XPS).
When the Si/N ratio in the main surface 10a of the resin film 10 is 8 or more, sufficient adhesion to the functional layer 20 described later can be obtained. From the viewpoint of adhesiveness, Si/N may be 9 or more, or 10 or more. The Si/N ratio is usually 50 or less, and may be 40 or less.
The thickness of the resin film 10 may be appropriately adjusted depending on the flexible device to which the laminate film 30 is applied, and may be 10 μm to 500 μm, 15 μm to 200 μm, or 20 μm to 100 μm. The resin film 10 of such a configuration can have particularly excellent bendability.
Next, an example of a method for producing the resin film 10 of the present embodiment will be described.
A polyimide varnish is prepared by dissolving a solvent-soluble polyimide polymerized by a known method for synthesizing a polyimide in a solvent. The solvent is not particularly limited as long as it dissolves the polyimide, and may be, for example, N-dimethylacetamide (DMAc), N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), γ -butyrolactone (GBL), or a combination thereof (mixed solvent).
In the case of producing a resin film containing an inorganic material (silicon material), the inorganic material is added to the polyimide-based polymer varnish, and the mixture is stirred and mixed by a known stirring method to prepare a dispersion in which the silicon material is uniformly dispersed.
The mixing ratio of the polyimide and the inorganic material in the polyimide-based polymer varnish or dispersion may be 1: 9 to 9: 1, or 3: 7 to 8: 2 in terms of mass ratio.
The polyimide-based polymer varnish or dispersion may further contain an additive. The additives may be selected from, for example, antioxidants, mold release agents, stabilizers, bluing agents, flame retardants, lubricants, and leveling agents. The polyimide-based polymer varnish or dispersion may contain a compound such as alkoxysilane having 1 or 2 or more metal alkoxide groups, which contributes to the formation of bonds between inorganic particles (silica particles, etc.). By using a dispersion containing such a compound, the proportion of inorganic particles can be increased while maintaining optical properties such as transparency of the resin film. Examples of such compounds include alkoxysilanes having an amino group.
Then, the dispersion is applied to a substrate by, for example, a known roll-to-roll or batch method to form a coating film. The coating film is dried to form a film. Thereafter, the film is peeled from the substrate, thereby obtaining the resin film 10. The substrate may be, for example, a polyethylene terephthalate (PET) substrate, a SUS tape, or a glass substrate.
The coating film may also be heated for drying and/or baking of the coating film. The coating film can be heated at a temperature of 50 to 350 ℃ under an inert atmosphere or under reduced pressure as appropriate. The solvent can be evaporated by heating the coating film. The resin film can also be formed by a method comprising drying the coating film at 50 to 150 ℃ and baking the dried coating film at 180 to 350 ℃.
Then, at least one main surface of the resin film may be subjected to surface treatment. The surface treatment may be a UV ozone treatment. By the UV ozone treatment, Si/N can be easily set to 8 or more. However, the method of setting Si/N to 8 or more is not limited to UV ozone treatment. In order to improve adhesion to a functional layer described later, the main surface 10a and/or 10b of the resin film 10 may be subjected to a surface treatment such as a plasma treatment or a corona discharge treatment.
The UV ozone treatment can be performed using a known ultraviolet light source containing a wavelength of 200nm or less. Examples of the ultraviolet light source include a low-pressure mercury lamp. As the ultraviolet light source, various towel selling devices provided with an ultraviolet light source may be used. An example of a commercially available apparatus is an Ultraviolet (UV) ozone cleaning apparatus UV-208 manufactured by Technevision.
The resin film 10 of the present embodiment thus obtained is excellent in bendability. In addition, when the atomic ratio of silicon atoms to nitrogen atoms, i.e., Si/N, is set to 8 or more in at least one main surface 10a, excellent adhesion to the functional layer 20 described later can be obtained.
[ second embodiment ]
Hereinafter, a laminated film according to a second embodiment will be described with reference to fig. 2.
Fig. 2 is a schematic cross-sectional view showing the laminated film of the present embodiment. In fig. 2, the same components as those of the resin film of the first embodiment shown in fig. 1 are denoted by the same reference numerals, and the description thereof is omitted.
The laminated film 30 of the present embodiment is basically composed of a resin film 10 and a functional layer 20 laminated on one main surface 10a of the resin film 10.
When the laminated film 30 is used as an optical member, a display member, or a front panel of a flexible device, the functional layer 20 may be a layer for further imparting a function (performance) to the laminated film 30. The functional layer 20 may be a layer having at least 1 function selected from the group consisting of ultraviolet absorption, surface hardness, adhesiveness, color tone adjustment, and refractive index adjustment.
The layer having a function of absorbing ultraviolet rays (ultraviolet ray absorbing layer) as the functional layer 20 is composed of a main material selected from, for example, an ultraviolet ray curing type transparent resin, an electron beam curing type transparent resin, and a thermosetting type transparent resin, and an ultraviolet ray absorber dispersed in the main material. By providing the ultraviolet absorbing layer as the functional layer 20, the change in the yellowness caused by light irradiation can be easily suppressed.
The ultraviolet-curable, electron beam-curable, or heat-curable transparent resin as a main material of the ultraviolet absorbing layer is not particularly limited, and may be, for example, poly (meth) acrylate.
The ultraviolet absorber may contain at least 1 compound selected from benzophenone-based compounds, salicylate-based compounds, benzotriazole-based compounds, and triazine-based compounds, for example.
In the present specification, the term "related compound" refers to a derivative of the compound to which the "related compound" is attached. For example, the "benzophenone-based compound" refers to a compound having benzophenone as a matrix skeleton and a substituent bonded to benzophenone. This is also true for other "family compounds".
The ultraviolet absorbing layer may be a layer that absorbs 95% or more of light having a wavelength of 400nm or less (for example, light having a wavelength of 313 nm). In other words, the ultraviolet absorbing layer may have a transmittance of less than 5% for light having a wavelength of 400nm or less (for example, light having a wavelength of 313 nm). The ultraviolet absorbing layer may contain an ultraviolet absorber at a concentration that can achieve such transmittance. The proportion of the ultraviolet absorber in the ultraviolet absorbing layer (functional layer 20) is usually 1 mass% or more, and may be 3 mass% or more, based on the mass of the ultraviolet absorbing layer, from the viewpoint of suppressing an increase in the yellowness of the laminated film caused by light irradiation. The proportion is usually 10 mass% or less, and may be 8 mass% or less.
The layer (hard coat layer) having a function of surface hardness (a function of exhibiting high hardness in the surface) as the functional layer 20 is, for example, a layer that gives a surface having pencil hardness higher than that of the surface of the resin film to the laminated film. The pencil hardness of the surface of the hard coat layer may be 2H or more, for example. The hard coat layer is not particularly limited, and contains an ultraviolet-curable, electron beam-curable, or heat-curable resin represented by poly (meth) acrylates. The hard coat layer may contain a photopolymerization initiator and an organic solvent. The poly (meth) acrylate is, for example, a poly (meth) acrylate formed from 1 or more (meth) acrylates selected from urethane (meth) acrylates, epoxy (meth) acrylates, and other polyfunctional poly (meth) acrylates, and contains monomer units derived from these monomers. The hard coat layer may contain an inorganic oxide such as silica, alumina, or polyorganosiloxane in addition to the above components.
The layer having an adhesive function (adhesive layer) as the functional layer 20 has a function of adhering the laminated film 30 to another member. As a material for forming the adhesive layer, a generally known material can be used. For example, a thermosetting resin composition or a photocurable resin composition may be used.
The adhesive layer may be composed of a resin composition containing a component having a polymerizable functional group. In this case, after the laminated film 30 is brought into close contact with another member, the resin composition constituting the adhesive layer is polymerized, whereby strong adhesion can be achieved. The adhesive strength between the resin film 10 and the adhesive layer may be 0.1N/cm or more, or 0.5N/cm or more.
The adhesive layer may contain a thermosetting resin composition or a photocurable resin composition as a material. In this case, the resin composition can be polymerized and cured by supplying energy after the polymerization.
The Pressure-Sensitive Adhesive layer may be a layer called a Pressure-Sensitive Adhesive (PSA) that is pressed and attached to an object. The pressure-sensitive adhesive may be a capsule type adhesive as "a material having adhesiveness at normal temperature and adhering to an adherend under a small pressure" (JIS K6800) or as "an adhesive capable of holding a specific component in a protective film (microcapsule) and maintaining stability before breaking the film by an appropriate method (pressure, heat, etc.)" (JIS K6800).
The layer having a function of color tone adjustment (color tone adjustment layer) as the functional layer 20 is a layer capable of adjusting the laminated film 30 to a desired color tone. The color tone adjusting layer is, for example, a layer containing a resin and a colorant. Examples of the colorant include inorganic pigments such as titanium oxide, zinc oxide, rouge, calcined titanium oxide pigments, ultramarine blue, cobalt aluminate, and carbon black; organic pigments such as azo-based compounds, quinacridone-based compounds, anthraquinone-based compounds, perylene-based compounds, isoindolinone-based compounds, phthalocyanine-based compounds, quinophthalone-based compounds, threne-based compounds, and pyrrolopyrroledione-based compounds; filling pigments such as barium sulfate and calcium carbonate; basic dyes, acid dyes, mordant dyes and the like.
The layer having a function of adjusting the refractive index (refractive index adjustment layer) as the functional layer 20 is a layer having a refractive index different from that of the resin film 10 and capable of giving a predetermined refractive index to the laminated film. The refractive index adjustment layer may be, for example, a suitably selected resin, a resin layer containing a pigment as the case may be, or a metal thin film.
Examples of the pigment for adjusting the refractive index include silicon oxide, aluminum oxide, antimony oxide, tin oxide, titanium oxide, zirconium oxide, and tantalum oxide. The average particle diameter of the pigment may be 0.1 μm or less. By setting the average particle diameter of the pigment to 0.1 μm or less, diffuse reflection of light transmitted through the refractive index adjustment layer can be prevented, and a decrease in transparency can be prevented.
Examples of the metal used for the refractive index adjustment layer include metal oxides and metal nitrides such as titanium oxide, tantalum oxide, zirconium oxide, zinc oxide, tin oxide, silicon oxide, indium oxide, titanium oxynitride, titanium nitride, silicon oxynitride, and silicon nitride.
The functional layer 20 suitably has the above-described function according to the use of the laminated film 30. The functional layer 20 may be a single layer or a plurality of layers. Each layer may have 1 function or more than 2 functions.
The functional layer 20 may have a function of surface hardness and ultraviolet absorption. In this case, the functional layer 20 may include "a single layer having a function of surface hardness and ultraviolet absorption", "a multilayer including a layer having surface hardness and a layer having ultraviolet absorption", or "a multilayer including a single layer having a function of surface hardness and ultraviolet absorption and a layer having surface hardness".
The thickness of the functional layer 20 may be appropriately adjusted according to a flexible device to which the laminated film 30 is applied, and may be, for example, 1 μm to 100 μm or 2 μm to 80 μm. The functional layer 20 is typically thinner than the resin film 10.
The laminated film 30 can be obtained by forming the functional layer 20 on the main surface 10a of the resin film 10. The functional layer 20 may be formed using a known roll-to-roll or batch method.
The ultraviolet absorbing layer as the functional layer 20 can be formed, for example, by applying a dispersion liquid containing an ultraviolet absorber and a main material such as a resin in which the ultraviolet absorber is dispersed on the main surface 10a of the resin film 10 to form a coating film, and drying and curing the coating film.
The hard coat layer as the functional layer 20 can be formed, for example, by a method of forming a coating film by applying a solution containing a resin for forming a hard coat layer on the main surface 10a of the resin film 10, and drying and curing the coating film.
The adhesive layer serving as the functional layer 20 can be formed, for example, by applying a solution containing an adhesive agent for forming an adhesive layer to the main surface 10a of the resin film 10 to form a coating film, and drying and curing the coating film.
The color-tone adjusting layer as the functional layer 20 can be formed, for example, by applying a dispersion liquid containing a pigment or the like forming the color-tone adjusting layer and a main material such as a resin in which the pigment or the like is dispersed on the main surface 10a of the resin film 10 to form a coating film, and drying and curing the coating film.
The refractive index adjustment layer as the functional layer 20 can be formed, for example, by applying a dispersion liquid containing inorganic particles or the like forming the refractive index adjustment layer and a main material such as a resin in which the inorganic particles or the like are dispersed on the main surface 10a of the resin film 10 to form a coating film, and drying and curing the coating film.
The single layer having the function of surface hardness and ultraviolet absorption as the functional layer 20 can be formed by a method of forming a coating film by applying a dispersion of a main material such as a resin containing an ultraviolet absorber or a resin in which an ultraviolet absorber is dispersed and a resin for forming a hard coat layer on the main surface 10a of the resin film 10, and drying and curing the coating film. The resin of the main material and the resin forming the hard coat layer may be the same.
The hard coat layer may be formed by applying a dispersion liquid containing an ultraviolet absorber and a main material such as a resin in which the ultraviolet absorber is dispersed on the main surface 10a of the resin film 10 to form a coating film, drying and curing the coating film to form an ultraviolet absorbing layer, applying a solution containing a resin for forming a hard coat layer on the ultraviolet absorbing layer to form a coating film, and drying and curing the coating film. With this method, a functional layer including a plurality of layers having a layer with surface hardness and a layer with ultraviolet absorption is formed.
A hard coat layer may be formed by applying a dispersion liquid containing an ultraviolet absorber, a main material such as a resin in which the ultraviolet absorber is dispersed, and a resin for forming a hard coat layer on the main surface 10a of the resin film 10 to form a coating film, drying and curing the coating film to form a single layer having a function of surface hardness and ultraviolet absorption, applying a solution containing the resin for forming the hard coat layer on the single layer to form a coating film, and drying and curing the coating film. By this method, a multi-layered functional layer including a layer having a function of surface hardness and ultraviolet absorption and a layer having surface hardness is formed.
The laminated film 30 of the present embodiment thus obtained has excellent bendability. The laminated film 30 may have functionalities such as transparency, ultraviolet ray resistance, and surface hardness required for application to an optical member, a display member, or a front panel of a flexible device. When the Si/N of the main surface 10a of the resin film 10 is 8 or more, the adhesion between the resin film 10 and the functional layer 20 is also excellent.
When a light irradiation test in which 313mm light is irradiated to the laminated film 30 for 24 hours from the functional layer 20 side is performed by a light source having an output of 40W provided at a distance of 5cm from the laminated film 30, the laminated film 30 may satisfy the following conditions:
(i) the laminated film after the light irradiation test has a transmittance of 85% or more and a haze of 1.0% or less with respect to light of 550mm, and
(ii) the laminated film before the light irradiation test has a yellowness (YI value) of 5 or less, and the difference in yellowness before and after the light irradiation test of the laminated film is less than 2.5.
The laminated film satisfying the conditions (i) and (ii) is less likely to change in contrast or color tone when bent, and can maintain good visibility.
For example, if a layer having a function of absorbing ultraviolet light is provided as the functional layer 20, and a material having a transmittance of 85% or more with respect to light of 550nm and a haze of 1.0% or less is used as the resin film 10 and the functional layer 20, a laminated film satisfying the conditions (i) and (ii) can be easily obtained.
The transmittance of the laminated film after the light irradiation test with respect to light of 550nm may be 90% or more, 100% or less, or 95% or less. The haze of the laminated film after the light irradiation test may be 0.9 or less, or 0.1 or more. The laminated film before the light irradiation test may have a transmittance of 85% or more with respect to light of 550nm and a haze value of 1.0 or less. The details of the measurement method of the transmittance and the haze are described in the examples below.
The yellowness of the laminated film before the light irradiation test may be 4 or less, 3 or less, or 0.5 or more. The yellowness before the light irradiation test was YI0The yellowness after light irradiation is YI1In this case, the difference Δ YI in yellowness before and after the light irradiation test of the laminated film can be represented by the following equation: Δ YI ═ YI1-YI0And (4) calculating. Δ YI is preferably 2.2 or less, may be 2.0 or less, and may be 0.1 or more. The details of the method for measuring the yellowness are described in the examples below.
In the present embodiment, the functional layer 20 is laminated on the one main surface 10a of the resin film 10, but the present invention is not limited thereto. For example, functional layers may be laminated on both surfaces of the resin film.
The laminated film 30 of the present embodiment is used as an optical member, a display member, or a front panel of a flexible device, for example.
[ third embodiment ]
A laminated film according to a third embodiment will be described below with reference to fig. 3.
Fig. 3 is a schematic cross-sectional view showing the laminated film of the present embodiment. In fig. 3, the same reference numerals are given to the same or corresponding components as those of the laminated film of the second embodiment shown in fig. 2, and the description thereof will be omitted. The laminated film 30 of the present embodiment is basically composed of a resin film 10, a functional layer 20 provided on one main surface 10a side of the resin film 10, and a primer layer 25 provided between the resin film 10 and the functional layer 20. The primer layer 25 is laminated on the one main surface 10a of the resin film 10. The functional layer 20 is laminated on a main surface (hereinafter, sometimes referred to as "one main surface") 25a of the primer layer 25 on the opposite side of the main surface that contacts the resin film 10.
The primer layer 25 is a layer formed of a primer, and preferably contains a material capable of improving adhesion to the resin film 10 and the functional layer 20. The compound contained in the primer layer 25 may be chemically bonded to a polyimide-based polymer or a silicon material contained in the resin film 10 at the interface.
Examples of the primer include ultraviolet-curable, thermosetting, and two-component curable epoxy compounds. The primer may also be a polyamic acid. These are preferable because they improve adhesion to the resin film 10 and the functional layer 20.
The primer may also contain a silane coupling agent. The silane coupling agent may be chemically bonded to the silicon material contained in the resin film 10 by a condensation reaction. The silane coupling agent is particularly useful when the compounding ratio of the silicon material contained in the resin film 10 is particularly high.
The silane coupling agent is a compound having an alkoxysilyl group having a silicon atom and 1 to 3 alkoxy groups covalently bonded to the silicon atom. The silane coupling agent may be a compound having a structure in which 2 or more alkoxy groups are covalently bonded to a silicon atom, or a compound having a structure in which 3 or more alkoxy groups are covalently bonded to a silicon atom. Examples of the alkoxy group include a methoxy group, an ethoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group. Among them, methoxy and ethoxy groups can improve reactivity with silicon materials.
The silane coupling agent may have a substituent having high affinity with the resin film 10 and the functional layer 20. The substituent of the silane coupling agent may be an epoxy group, an amino group, a ureido group, or an isocyanate group, from the viewpoint of affinity with the polyimide-based polymer contained in the resin film 10. In the case where the functional layer 20 contains (meth) acrylates, if the silane coupling agent used in the primer layer 25 has an epoxy group, a methacryloyl group, an acryloyl group, an amino group, or a styryl group, the affinity tends to be improved. Among them, silane coupling agents having a substituent selected from the group consisting of a methacryloyl group, an acryloyl group, and an amino group tend to have excellent affinity with the resin film 10 and the functional layer 20.
The thickness of the primer layer 25 may be appropriately adjusted according to the functional layer 20, and may be 0.01nm to 20 μm. In the case of using an epoxy-based compound primer, the thickness of the primer layer 25 may be 0.01 to 20 μm, or 0.1 to 10 μm. In the case of using the silane coupling agent, the thickness of the primer layer 25 may be 0.1nm to 1 μm, or 0.5nm to 0.1 μm.
Next, a method for producing the laminated film 30 of fig. 3 according to the present embodiment will be described.
First, the resin film 10 is produced in the same manner as in the first embodiment. Then, a solution in which a primer is dissolved is applied to one main surface 10a of the resin film 10 by a known roll-to-roll or batch method to form a first coating film. If necessary, the first coating film may be slightly cured.
Then, as in the first embodiment, a raw material of the functional layer 20 is applied to the first coating film to form a second coating film. The primer layer 25 and the functional layer 20 are formed by curing the first coating film and the second coating film simultaneously or separately, thereby obtaining a laminated film 30.
The laminated film 30 of the present embodiment thus obtained has excellent bendability. Since the primer layer 25 is provided between the resin film 10 and the functional layer 20, the adhesion between the resin film 10 and the functional layer 20 is high. The laminated film 30 may have functionality such as transparency, ultraviolet ray resistance, and surface hardness required for application to an optical member, a display member, and a front panel of a flexible device.
In the present embodiment, the case where the functional layer 20 is provided on the side of the one main surface 10a of the resin film 10 and the primer layer 25 is provided between the resin film 10 and the functional layer 20 is exemplified, but the present invention is not limited thereto. The functional layer may be laminated on both sides of the resin film with a primer layer interposed therebetween.
[ fourth embodiment ]
Hereinafter, a display device according to a fourth embodiment will be described with reference to fig. 4.
Fig. 4 is a schematic cross-sectional view showing an example of a display device as an application example of the laminated film of the present embodiment. The display device 100 of the present embodiment includes the organic EL device 50, the touch sensor 70, and the front panel 90. They are typically housed in a housing. The organic EL device 50 and the touch sensor 70, and the touch sensor 70 and the front panel 90 are bonded with an Optical Clear Adhesive (OCA), for example.
The organic EL device 50 includes an organic EL element 51, a first substrate 55, a second substrate 56, and a sealing material 59.
The organic EL element 51 includes a pair of electrodes (a first electrode 52 and a second electrode 53) and a light-emitting layer 54. The light emitting layer 54 is disposed between the first electrode 52 and the second electrode 53.
The first electrode 52 is formed of a conductive material having light transmittance. The second electrode 53 may also have optical transparency. As the first electrode 52 and the second electrode 53, a known material can be used.
The light-emitting layer 54 can be formed using a known light-emitting material constituting an organic EL element. The light-emitting material may be any of a low molecular compound and a high molecular compound.
When power is supplied between the first electrode 52 and the second electrode 53, carriers (electrons and holes) are supplied to the light-emitting layer 54, and light is generated in the light-emitting layer 54. The light generated in the light-emitting layer 54 passes through the first electrode 52 and the first substrate 55 and is emitted to the outside of the organic EL device 50.
The first substrate 55 is formed of a material having light transmittance. The second substrate 56 may have a light-transmitting property. The first substrate 55 and the second substrate 56 are bonded together with a sealing material 59 disposed so as to surround the organic EL element. The first substrate 55, the second substrate 56, and the sealing material 59 form a sealing structure that seals the organic EL element therein. The first substrate 55 and/or the second substrate 56 are mostly a gas barrier material.
As a material for forming one or both of the first substrate 55 and the second substrate 56, an inorganic material such as glass or a known transparent resin such as an acrylic resin can be used. As these members, the laminated film of the present embodiment described above may be used.
The first substrate 55 and the second substrate 56, which can be formed using the laminated film of the present embodiment, correspond to the display member or the gas barrier material of the present embodiment. The organic EL device 50 having the first substrate 55 and the second substrate 56 is excellent in flexibility because the laminated film of the present embodiment is used.
The touch sensor 70 includes a substrate 71 (touch sensor base material), and an element layer 72 having a detection element formed on the substrate 71.
The substrate 71 is made of a material having light transmittance. As the substrate 71, an inorganic material such as glass or a known transparent resin such as an acrylic resin can be used. The laminated film of the present embodiment described above may be used as the substrate 71.
A known detection element including a semiconductor element, a wiring, a resistor, and the like is formed in the element layer 72. As the configuration of the detection element, a configuration of a known detection system can be realized by using a matrix switch, a resistive film system, an electrostatic capacitance system, or the like.
The substrate 71 to which the laminated film of the present embodiment can be applied corresponds to the optical member of the present embodiment. The touch sensor 70 having such a substrate 71 is excellent in flexibility because the laminated film of the present embodiment is used.
The front panel 90 is formed of a material having light transmittance. The front panel 90 is located on the outermost layer of the display device on the display screen side, and functions as a protective member for protecting the display device. The front panel is sometimes also referred to as a window film. As the front panel 90, an inorganic material such as glass or a known transparent resin such as acrylic resin can be used. The laminate film of the present embodiment described above may be used as the front panel 90. When a laminated film is used as the front panel 90, the laminated film is generally disposed in such a direction that the functional layer is located outside the display device.
The front panel 90 to which the laminated film of the present embodiment can be applied corresponds to the optical member of the present embodiment. The front panel 90 is excellent in bendability because of the use of the laminate film of the present embodiment.
If the display device 100 employs the laminate film of the present embodiment as 1 or more constituent members selected from the organic EL device 50, the touch sensor 70, and the front panel 90, it can have excellent flexibility as a whole. That is, the display apparatus 100 may be a flexible device.
An apparatus (flexible device) to which the laminated film of this embodiment can be applied is not limited to the above-described display apparatus. For example, the present invention may be applied to a solar cell including a substrate on which a photoelectric conversion element is formed and a front panel provided on a surface of the substrate. In this case, if the laminated film of the present embodiment is used as a substrate or a front panel of a solar cell, the solar cell can have excellent flexibility as a whole.
[ examples ]
The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to the following examples.
Study 1-
Example 1
According to known documents (for example, United States Patent; Patent No. US8, 207, 256B2), a resin film containing polyimide and silica particles (silica particle content: 60 mass%) was produced as follows.
An acid anhydride of the formula (1), a diamine of the formulae (2) and (3), a catalyst, and a solvent (γ -butyrolactone and dimethylacetamide) were charged into a polymerization vessel purged with nitrogen. The amounts of the acid anhydride represented by the formula (1) and the diamine represented by the formula (2) were 75.0g, the diamine represented by the formula (3) was 76.4g, the catalyst was 1.5g, gamma-butyrolactone 438.4g, and dimethylacetamide was 313.1 g. (2) The molar ratio of the diamine of the formula (II) to the diamine of the formula (3) was 3: 7, and the molar ratio of the total of the diamines to the acid anhydride was 1.00: 1.02.
Chemistry 5
After the mixture in the polymerization vessel was stirred to dissolve the raw materials in the solvent, the mixture was heated to 100 ℃ and then to 200 ℃ and the temperature was maintained for 4 hours to polymerize the polyimide. In this heating, water is removed from the liquid. Thereafter, the polyimide was purified and dried to obtain polyimide.
Then, a gamma butyrolactone solution of polyimide having a concentration adjusted to 20 mass%, a dispersion in which silica particles having a solid content concentration of 30 mass% were dispersed in gamma butyrolactone, and a dimethylacetamide solution of alkoxysilane having an amino group were mixed, and stirred for 30 minutes.
Here, the mass ratio of the silica particles to the polyimide was set to 60: 40, and the amount of the alkoxysilane having an amino group was set to 1.67 parts by mass with respect to 100 parts by mass of the total of the silica particles and the polyimide.
The mixed solution was applied to a glass substrate, heated at 50 ℃ for 30 minutes and at 140 ℃ for 10 minutes to dry the solvent. Thereafter, the film was peeled off from the glass substrate, and a metal frame was mounted and heated at 210 ℃ for 1 hour, thereby obtaining a resin film having a thickness of 80 μm.
A two-component curable primer (trade name: ARACOAT AP2510, available from Seikagawa chemical industries, Ltd.) was applied to one surface of the obtained resin film to form a coating film, and the coating film was dried and cured to form a primer layer having a thickness of 1 μm.
Then, a solution for forming a functional layer was applied on the primer layer to form a coating film, and the coating film was dried and cured to form a functional layer (a layer having a function of surface hardness and ultraviolet absorption) having a thickness of 10 μm, thereby obtaining a laminated film of example 1. A solution for forming a functional layer was prepared by mixing and stirring 47.5 parts by mass of a 4-functional acrylate (trade name: A-TMMT, manufactured by Newzhongcun Chemical Co., Ltd.), 47.5 parts by mass of a 3-functional acrylate (trade name: A-TMPT, manufactured by Newzhongcun Chemical Co., Ltd.), 12.5 parts by mass of a reactive urethane polymer (trade name: 8BR-600, manufactured by grand Fine Chemical Co., Ltd., 40% by mass), 3 parts by mass of a triazine-based ultraviolet absorber (TINUVIN (registered trademark) 479, manufactured by BASF Co., Ltd.), 8 parts by mass of a photopolymerization initiator (IRGACURE (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.6 part by mass of a leveling agent (trade name: BYK-350, manufactured by BYK Chemie Japan Co., Ltd.), and 107 parts by mass of methyl ethyl ketone.
Comparative example 1
A functional layer having a thickness of 10 μm was formed on one main surface of a substrate (PMMA film) made of polymethyl methacrylate (PMMA) having a thickness of 120 μm in the same manner as in example 1, to obtain a laminated film of comparative example 1.
(evaluation) measurement of Pencil hardness
The pencil hardness of the surface on the functional layer side of the laminated films of example 1 and comparative example 1 was measured in accordance with JIS K5600-5-4. The load in the measurement of pencil hardness was set to 1 kg. The results are shown in table 1.
Evaluation of bendability
The laminated films of example 1 and comparative example 1 were cut into a size of 1cm × 8 cm. The functional layer of the cut laminate film was wound on a roll having a radius r of 1mm with the surface of the functional layer facing the inside, and the presence or absence of cracks in the laminate film was confirmed. The bendability was determined based on the following criteria. The results are shown in table 1.
A: no cracks were generated, and good appearance was maintained.
C: more than 5 cracks were generated.
Optical Property yellowness index (YI value)
The yellowness (Yellow Index: YI value) of the laminated films of example 1 and comparative example 1 was measured by an ultraviolet-visible near-infrared spectrophotometer V-670 manufactured by JASCO corporation. After the background measurement was performed in the absence of the sample, the laminated film was set in a sample holder, and the transmittance for light of 300nm to 800nm was measured to determine the 3 stimulus value (X, Y, Z). The YI value was calculated based on the following equation.
YI value of 100X (1.28X-1.06Z)/Y
The optical characteristics were determined based on the following criteria. The results are shown in table 1.
A: YI value less than 3
C: YI value of 3 or more
Transmittance of light
The transmittance for light of 300nm to 800nm was measured using an ultraviolet-visible near-infrared spectrophotometer V-670 manufactured by Japan Spectroscopy. The transmittance was determined based on the following criteria. The results are shown in table 1.
A: has a transmittance of 90% or more with respect to light having a wavelength of 550nm
C: the transmittance of light at a wavelength of 550nm is less than 90%
Haze degree
The haze of the laminated film was measured by placing the laminated film in a sample holder using a fully automatic direct haze computer HGM-2DP manufactured by Suga tester. Haze was determined based on the following criteria. The results are shown in table 1.
A: haze (%) less than 1.0%
C: haze (%) of 1.0% or more
Ultraviolet ray aging acceleration test (QUV test, light irradiation test)
The laminated film was used for a QUV test using UVCON manufactured by Atras Co. The light source was UV-B313 nm, the output was 40W, and the distance between the sample (laminated film) and the light source was set to 5 cm. The laminated film was irradiated with ultraviolet rays for 24 hours from the functional layer side.
After the ultraviolet irradiation, the optical characteristics (YI value, transmittance) were evaluated as described above. The results are shown in table 1.
[ Table 1]
From the results in table 1, the multilayer film of example 1 was excellent in bendability. It is also understood that the laminated film of example 1 has functions such as ultraviolet ray resistance and surface hardness, and can be used for an optical member, a display member, and a front panel of a flexible device.
Study 2-
Example 2
Using the same polyimide as in example 1, a γ butyrolactone solution of polyimide having a concentration adjusted to 20 mass% was prepared. This solution, a solution in which silica particles having a solid content concentration of 30 mass% were dispersed in gamma butyrolactone, a dimethylacetamide solution of an alkoxysilane having an amino group, and water were mixed and stirred for 30 minutes.
Here, the mass ratio of silica particles to polyimide was set to 60: 40, the amount of alkoxysilane having an amino group was set to 1.67 parts by mass with respect to 100 parts by mass of the total of silica particles and polyimide, and the amount of water was set to 10 parts by mass with respect to 100 parts by mass of the total of silica and polyimide.
Using the obtained mixed solution, a laminated film having a resin film, a primer layer, and a functional layer, which were laminated in this order, was obtained in the same manner as in example 1. However, the thickness of the functional layer was changed to 6 μm.
Example 3
A polyimide having a glass transition temperature of 390 ℃ was prepared ("NEOPULIM" manufactured by Mitsubishi gas chemical corporation). A gamma butyrolactone solution having a polyimide concentration of 20 mass%, a dispersion in which silica particles having a solid content concentration of 30 mass% were dispersed in gamma butyrolactone, a dimethylacetamide solution of an alkoxysilane having an amino group, and water were mixed, and stirred for 30 minutes to obtain a mixed solution. The mass ratio of the silica particles to the polyimide was 55: 45, the amount of the alkoxysilane having an amino group was 1.67 parts by mass with respect to 100 parts by mass of the total of the silica particles and the polyimide, and the amount of water was 10 parts by mass with respect to 100 parts by mass of the total of the silica particles and the polyimide. Using this mixed solution, a laminated film of example 3 having a resin film, a primer layer, and a functional layer (thickness 10 μm) laminated in this order was obtained in the same manner as in example 1.
Comparative example 2
The resin film of example 2 before forming the primer layer and the functional layer was evaluated as the film of comparative example 2.
(evaluation) optical Properties
The films of example 2 and comparative example 2 were used for the same QUV test (light irradiation test) as in study 1. The transmittance, YI value and haze were measured for the films before and after the test in the same manner as in study 1. The difference AYI between YI values before and after the test was also determined. The results are shown in table 2.
Observability of
The film before the light irradiation test was bent, and the state of appearance such as contrast and color tone at that time was confirmed, and the observability was determined based on the following criteria. The results are shown in table 2.
A: no change in contrast and hue was observed.
C: appearance changes such as changes in contrast and color tone were observed.
[ Table 2]
As shown in table 2, the laminated film of example 2 used in the light irradiation test satisfied the above-described conditions (i) and (ii), and it was confirmed that the laminated film had high observability when bent.
Study 3-
Example 4
A resin film having a thickness of 75 μm and containing polyimide and silica particles (silica particle content: 60% by mass) was produced in the same manner as in example 1.
One main surface of the resin film was subjected to UV ozone treatment. The UV ozone treatment was carried out for 15 minutes using an Ultraviolet (UV) ozone cleaning apparatus UV-208 manufactured by Technevision.
Then, a silane coupling agent (3-aminopropyltriethoxysilane, trade name: Z6011, manufactured by Dow Corning Toray Co., Ltd.) having an amino group was applied to the principal surface of the resin film subjected to UV ozone treatment to form a primer layer.
Then, a solution for forming a functional layer was applied on the primer layer to form a coating film, and the coating film was dried and cured to form a functional layer (a layer having a function of surface hardness and ultraviolet absorption) having a thickness of 5 μm, thereby obtaining a laminated film of example 3. A solution for forming a functional layer was prepared by mixing and stirring 47.5 parts by mass of a 4-functional acrylate (trade name: A-TMMT, manufactured by Newzhongcun Chemical Co., Ltd.), 47.5 parts by mass of a 3-functional acrylate (trade name: A-TMPT, manufactured by Newzhongcun Chemical Co., Ltd.), 12.5 parts by mass of a reactive urethane polymer (trade name: 8BR-600, manufactured by Fine Chemical Co., Ltd., 40% by mass), 3 parts by mass of a triazine-based ultraviolet absorber (TINUVIN (registered trademark) 479, manufactured by BASF Co., Ltd.), 8 parts by mass of a photopolymerization initiator (IRGACURE (registered trademark) 184, manufactured by Ciba Specialty Chemicals Co., Ltd.), 0.6 part by mass of a leveling agent (trade name: BYK-350, manufactured by BYK Chemie Japan Co., Ltd.), and 107 parts by mass of methyl ethyl ketone.
Reference example
A resin film having a thickness of 75 μm and containing polyimide and silica particles (silica particle content: 60% by mass) was produced in the same manner as in example 1.
Then, a silane coupling agent having an amino group (3-aminopropyltriethoxysilane, trade name: Z6011, manufactured by Dow Coming Toray Co., Ltd.) was applied onto one main surface of the resin film to form a primer layer.
Then, the same functional layer as in example 3 was formed on the primer layer to obtain a laminated film of a reference example.
Evaluation of surface composition of resin film
The surface of the resin film of example 3 subjected to UV ozone treatment and one main surface of the resin film of the reference example were evaluated by X-ray photoelectron spectroscopy (XPS).
In the X-ray photoelectron spectroscopy, an X-ray photoelectron spectrometer (trade name: Quantera SXM, manufactured by ULVAC PHI) was used. AlKa (1486.6eV) with a diameter of 100 μm was used as the X-ray. For charge compensation, an electron gun 1eV and an Ar ion gun 10eV were used. The photoelectron exit angle was set to 75 °.
Using the device-attached analysis software: the XPS spectrum obtained by the Multipak V8.2C was used to determine the peak area of each element, and the amount of each element on the film surface was calculated in atom% units from the peak area. Then, the atomic ratio of silicon atoms to nitrogen atoms (Si/N) was calculated from the Si2p peak and the N1s peak. The results are shown in table 3.
Haze degree
The haze (%) of the laminated film was evaluated in the same manner as in study 1. The results are shown in table 4.
[ Table 3]
| C1s | N1s | O1s | Si2p | Si/N | |
| Example 4 | 22 | 2.3 | 56 | 19 | 8.3 |
| Reference example | 50 | 2.0 | 35 | 13 | 6.5 |
(unit: atm%)
[ Table 4]
| Haze degree | |
| Example 4 | A |
| Reference example | A |
As shown in table 3, the ratio of silicon atoms to nitrogen atoms, i.e., Si/N, in the surface of the resin film of example 4 subjected to UV ozone treatment was 8.3. On the other hand, it is found that Si/N is 6.5 on one surface of the resin film of the reference example.
Evaluation of adhesion of functional layer
The functional layers of the laminated films of examples and reference examples were evaluated for adhesion by a Cross cut test in accordance with JIS-K5600-5-6. The number of scars formed in a 10 × 10 checkered pattern at 2mm intervals was counted by sticking CELLOTAPE (registered trademark, manufactured by Nichiban) to the surface and pulling away the CELLOTAPE in a direction of 60 ° from the surface. The adhesion was determined based on the following criteria. The results are shown in table 3.
A: the number of the remaining chequers is 100
C: the number of the remaining checkerboards is below 99
[ Table 5]
| Evaluation of adhesion | |
| Example 4 | A |
| Reference example | C |
As is clear from the results in table 5, the functional layer of the multilayer film of example 4 had high adhesion, and the functional layer of the multilayer film of the reference example had low adhesion.
Description of the symbols
10 resin films, 20 functional layers, 25 primer layers, 30 laminated films, 50 organic EL devices, 70 touch sensors, 90 front panels, 100 display devices.
Claims (13)
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
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| JP2014-228100 | 2014-11-10 | ||
| JP2014228100 | 2014-11-10 | ||
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| JP2014228099 | 2014-11-10 | ||
| JP2015-145176 | 2015-07-22 | ||
| JP2015145176A JP6482977B2 (en) | 2014-11-10 | 2015-07-22 | Laminated film for flexible device, optical member, display member, front plate, and method for producing laminated film for flexible device |
| CN201580060423.5A CN107635772B (en) | 2014-11-10 | 2015-11-06 | Resin film, laminated film, optical member, display member, front panel, and method for producing laminated film |
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| CN201910554296.4A Pending CN110171176A (en) | 2014-11-10 | 2015-11-06 | The manufacturing method of resin film, stacked film, optical component, display member, front panel and stacked film |
| CN201580060423.5A Active CN107635772B (en) | 2014-11-10 | 2015-11-06 | Resin film, laminated film, optical member, display member, front panel, and method for producing laminated film |
| CN202110045625.XA Pending CN112810271A (en) | 2014-11-10 | 2015-11-06 | Resin film, laminated film, optical member, display member, front panel, and method for producing laminated film |
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| CN201580060423.5A Active CN107635772B (en) | 2014-11-10 | 2015-11-06 | Resin film, laminated film, optical member, display member, front panel, and method for producing laminated film |
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| US (1) | US20170334180A1 (en) |
| JP (3) | JP6482977B2 (en) |
| KR (2) | KR102318433B1 (en) |
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| KR102610461B1 (en) * | 2016-08-23 | 2023-12-06 | 린텍 가부시키가이샤 | hard coat film |
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| CN107635772A (en) | 2018-01-26 |
| KR101994562B1 (en) | 2019-06-28 |
| TWI674199B (en) | 2019-10-11 |
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